JP2649967B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inert and easily decolorized in the course of photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a solid fine particle dispersion of a dye to be eluted.

(Prior Art) In a silver halide photographic material, a photographic emulsion layer and other hydrophilic colloid layers are often colored in order to absorb light in a specific wavelength range.

When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, the filter layer may be located between them.

An image based on light scattered when passing through or after transmission through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the photosensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. For the purpose of preventing blurring or halation, a colored layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. When there are a plurality of photographic emulsion layers, an anti-halation layer may be provided between the layers.

Coloring of the photographic emulsion layer is also performed to prevent a reduction in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation).

These hydrophilic colloid layers to be colored usually contain a dye. This dye must satisfy the following conditions.

(1) To have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer is adversely affected in a chemical sense,
For example, do not give a decrease in sensitivity, regression of latent images, or fog.

(3) No decoloration during the photographic processing or elution into the processing solution or washing water, leaving no harmful coloring on the processed photographic light-sensitive material.

(4) Do not diffuse from the dyed layer to other layers.

(5) It has excellent stability over time in a solvent or a photographic material and does not discolor.

Many proposals have been made to find a dye satisfying the above conditions. For example, JP-A-52-135335, JP-A-63-316853
The oxonol dye having a pyrazolopyridine nucleus described in (1) satisfies the above conditions (1), (2), (3) and (5) and has excellent properties as an irradiation preventing dye.

However, especially when the colored layer is a filter layer or an anti-halation layer on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. In many cases, it is necessary to make the coloring substantially inaccessible, and the condition (4) is important. This is because otherwise, not only does it have a detrimental spectral effect on the other layers, but also its effect as a filler layer or antihalation layer is diminished. Therefore, the above-mentioned oxonol dye having a pyrazolopyridine nucleus was not always sufficient under the condition (4). More efforts have been made in the past to prevent such dye diffusion.

For example, U.S. Pat.No. 2,548,564 discloses a method in which a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye is coexisted in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. , 4,124,386, 3,625,
No. 694 and the like.

Further, a method of dyeing a specific layer by using a dye solid insoluble in water is disclosed in JP-A-56-12639, JP-A-52-92716, and JP-A-55-92716.
155350, 55-155351, 63-27838, 63-197
943, European Patent Nos. 15,601, 274,723, 276,566
No. 299,435, U.S. Pat. No. 4,803,150, and International Application Publication (WO) 88/04794.

Further, a method of dyeing a specific layer using metal salt fine particles having a dye adsorbed thereto is disclosed in U.S. Pat.Nos. 2,719,088 and 2,496,841.
No. 2,496,843, and JP-A-60-45237.

However, even with the use of these improved methods, various factors such as speeding up of processing, improvement of the processing solution composition, and improvement of the photographic emulsion composition due to the slow decolorization and / or elution rate of the dye during the development processing. However, it was difficult to eliminate the residual color contamination due to the dye when the color was changed.

[Problems to be solved by the invention]

Accordingly, an object of the present invention is to selectively dye only a specific layer in a photographic light-sensitive material, and further contain a solid fine particle-dispersed dye which rapidly decolorizes and / or elutes during development processing. It is to provide.

[Means for solving the problem]

As a result of various studies by the present inventors, an object of the present invention is to provide a silver halide photographic material having a hydrophilic colloid layer containing a solid fine particle dispersion of a compound represented by the following general formula (I). And what can be achieved.

General formula (I) Wherein R ₁ is p-carboxyphenyl, m-carboxyphenyl, o-carboxyphenyl, 3,5-dicarboxyphenyl, 2,4-dicarboxyphenyl, 2,5-dicarboxyphenyl Enyl, p-carboxybenzyl, m-carboxybenzyl, o-carboxybenzyl, a group selected from the group consisting of p-carboxyphenethyl and 2,4-dicarboxybenzyl, wherein R ₂ is a hydrogen atom, an alkyl group, an aryl group Represents a heterocyclic group, COR ₄ or SO ₂ R ₄ ;
₃ is a hydrogen atom, a cyano group, a hydroxyl group, a carboxylic acid group, an alkyl group, an aryl group, COOR ₄ , OR ₄ , NR ₅ R ₆ , CONR ₅ R ₆ , NR
₅ COR ₄ , NR ₅ SO ₂ R ₄ or NR ₅ CONR ₅ R ₆ (where R ₄ represents an alkyl group or an aryl group, and R ₅ and R ₆ represent a hydrogen atom, an alkyl group or an aryl group.) , L ₁ , L ₂ ,
L ₃ or represents a methine group, an n1 or 2. It is preferable that the compound represented by the general formula (I) of the present invention is substantially water-insoluble at pH 6 or lower, and is water-insoluble at pH 8 or higher.

It is particularly preferable that the compound represented by the general formula (I) of the present invention does not have a sulfonic acid group or a salt thereof or a salt of a carboxylic acid group.

Hereinafter, the compound represented by formula (I) will be described in detail.

The alkyl group represented by R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is an alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl,
n-propyl, n-butyl, n-hexyl, n-decyl, isopropyl, isobutyl, t-butyl) and a substituent [for example, a hydroxyl group, a carboxylic acid group, a cyano group, a nitro group, a halogen atom, (for example, Chlorine, bromine,
Fluorine), an alkoxy group (eg, methoxy, ethoxy), an aryl group (eg, phenyl, p-carboxyphenyl, p-hydroxyphenyl, p-methylsulfamoylphenyl), an amino group (eg, dimethylamino) , Diethylamino), acylamino groups (eg, acetylamino, benzoylamino), sulfonamide groups (eg, tansulfonamide, benzenesulfonamide), carbomoyl groups (eg, methylcarbamoyl,
Ethylcarbamoyl, phenylcarbamoyl) and a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The aryl group represented by R ₂ , R ₃ , R ₄ , R ₅ or R ₆ represents a phenyl group or a naphthyl group, and has a substituent [eg, a hydroxyl group, a carboxyl group, a sulfonamide group (eg, methanesulfonamide, benzene Sulfonamides), acylamino groups (eg, acetylamino, pivaloylamino, benzoylamino), sulfamoyl groups (eg,
Methylsulfamoyl, ethylsulfamoyl, phenylsulfamoyl), carbamoyl group (for example, methylcarbamoyl, ethylcarbamoyl, phenylcarbamoyl), ureido group (for example, 3-methylureido, 3
-(P-carboxyphenyl) ureido), a cyano group,
Nitro group, halogen atom (eg, chlorine, bromine, fluorine), alkyl group (eg, methyl, ethyl, n-propyl, t-butyl, isopropyl), alkoxy group (eg, methoxy, ethoxy), ester group (eg, , Methoxycarbonyl, ethoxycarbonyl, acetyloxy), and an amino group (eg, dimethylamino, diethylamino)].

The heterocyclic group represented by R ₂ is a 5- or 6-membered nitrogen-containing heterocyclic group having at least one nitrogen atom (for example, pyridin-2-yl, quinolin-2-yl, benzothiazol-2-yl , Benzoxazol-2-yl, pyrimidin-2-yl), a substituent [for example, a carboxy group, a hydroxyl group, a sulfonamide group (for example, benzenesulfonamide, methanesulfonamide), an acylamino group (for example, benzoylamino, p-cyanobenzoylamino)].

The methine group represented by L ₁ , L ₂ or L ₃ has not only an unsubstituted methine group but also a substituent (eg, methyl, ethyl, benzyl, phenyl, carboxylic acid, cyano, fluorine, chlorine) And a methine group is connected to form a ring (for example, And those which form

In the general formula (I), R ₁ represents a phenyl group or an aralkyl group having at least one carboxylic acid group. R ₁
Is a p-carboxyphenyl group, an m-carboxyphenyl group, an o-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 2,4-dicarboxyphenyl group, a 2,5-dicarboxyphenyl group. Enyl group, p-carboxybenzyl group, m-
Carboxybenzyl group, o-carboxybenzyl group, p
A carboxyphenethyl group and a 2,4-dicarboxybenzyl group.

Hereinafter, specific examples of the compound represented by Formula (I) will be described, but the present invention is not limited thereto.

Specific examples (I-1) to (I-30) show the substituents of general formula (I) in a specific manner.

The dye represented by formula (I) is described in, for example, JP-B-39-22.
No. 069, No. 43-3504, No. 52-38056, No. 54-38129,
No. 55-10059, No. 58-35544, JP-A-49-99620,
Nos. 59-16834 and 63-316853 or U.S. Pat.
It can be synthesized using the method described in JP-A-81,225 and the like.

Synthesis Example 1 (Synthesis of Compound I-2) 4-Methyl-7-hydroxyethyl-2- (4-carboxyphenyl) pyrazolo [3,4-b] pyridine-3,6-
A mixture of 6.3 g of dione, 2.2 g of malonaldehyde dianyl, 2.8 ml of triethylamine, 20 ml of methanol, and 2.4 g of acetic anhydride was stirred at room temperature for 10 hours, then, 50 ml of acetic acid was added, and the mixture was further stirred for 1 hour. The precipitated crystals were collected. After dissolving the obtained crystals in N, N-dimethylformamide, ethanol was added and the resulting precipitate was collected to give Compound I.
-3 as a dark blue powder. λ _max = 656 nm (methanol containing triethylamine (2%)) Synthesis Example 2 (Synthesis of Compound I-5) 4,7-Dimethyl-2- (4-carboxyphenyl) pyrazolo [3,4, b] pyridine-3 5,6-dione 5.1 g, glutaconaldehyde dianyl hydrochloride 2.8 g, triethylamine 7 m
l, a mixture of 2,4 g of acetic anhydride and 30 ml of N, N-dimethylformamide was stirred at room temperature for 5 hours. Acetic acid (60 ml) was added to the reaction solution, and the mixture was stirred for 1 hour. After dissolving the obtained crystals in N, N-dimethylformamide, isopropanol is added and the resulting precipitate is collected to obtain I.
0.9 g of -6 was obtained as a dark blue powder. λ _max = 752 nm (methanol containing triethylamine (2%)) Generally, the compound of the general formula (I) has an area of 1 m ² on the photosensitive material.
It is used in an amount of about 1 to 1000 mg per day. Preferably, about 1 m ² per 1～800Mg.

When the compound represented by the general formula (I) is used as a filter dye or an antihalation dye, any effective amount can be used.
Preferably, it is used so as to be in the range of 3.5. The timing of addition may be any step before coating.

The compounds of the general formula (I) according to the invention can be used in both emulsion layers and other hydrophilic colloid layers.

The fine particle dispersion of the compound of the general formula (I) of the present invention comprises a method of precipitating the compound of the present invention in the form of a dispersion, and / or
Alternatively, in the presence of a dispersing agent, a method of forming by a known pulverizing means such as ball milling (ball mill, vibrating ball mill, planetary ball mill, etc.) sand milling, colloid milling, jet milling, roller milling, etc. (Water, alcohol, etc.) may or may not be allowed to coexist. Alternatively, after dissolving the compound of the present invention in a suitable solvent, a poor solvent for the compound of the present invention may be added to precipitate microcrystalline powder, in which case a surfactant for decomposition may be used. Good. Alternatively, by controlling the pH of the compound of the present invention, the compound is first dissolved and then the pH is adjusted.
May be changed for microcrystallization.

Fine particles of the compound of the present invention in the dispersion, the average particle size is 10
It is more preferably 2 μm or less, particularly preferably 0.5 μm or less, and even more preferably 0.1 μm or less in some cases.

As the hydrophilic colloid, gelatin is typical, but any other conventionally known colloids usable for photography can be used.

The silver halide emulsion and the light-sensitive material used in the silver halide photographic light-sensitive material of the present invention will be described in detail.

The silver halide emulsion used in the present invention is preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide or silver chloride.

The silver halide grains used in the present invention have a regular crystal form such as cubic or octahedral, or irregular such as spherical or plate-like.
Or a complex form of these crystal forms. Although a mixture of particles of various crystal forms can be used, it is preferable to use a regular crystal form.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer or may consist of a uniform phase. Also, grains whose latent image is mainly formed on the surface (eg, a negative emulsion) may be formed, and grains whose main image is mainly formed inside the grains (eg, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) May be used. Preferably, the particles are such that the latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
Micron or less, preferably 0.3 micron or less, preferably 0.6 micron or more in diameter, with an average aspect ratio of 5
Either a tabular grain emulsion in which the above grains occupy 50% or more of the total projected area, or a statistical variation coefficient (standard deviation S is divided by diameter in a distribution expressed by diameter when the projected area is approximated by a circle) Monodisperse emulsions having a value S /) of not more than 20% are preferred. Further, two or more kinds of the average grain emulsion and the monodispersed emulsion may be mixed.

The photographic emulsion used in the present invention is Chimie er Physique Photographeque by P. Glafkides.
(Paul Montell, 1967), GFDuffin, Photographic Emulsion, Chemistry (Photographic Emulsion Chemistr)
y) (Focal Press, 1966), VLZelikman et al., Making and
Coating Photographic Emulsion (Ma
king and Coating Photographic Emulsion) (Focal Press, 1964) and the like.

In forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574,6
No. 28, No. 3,704,130, No. 4,297,439, No. 4,276,
No. 374) and thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-77737, and amine compounds (for example, JP-A-54-100717).

In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisted.

As a binder or protective colloid that can be used in the emulsion phase or the intermediate layer of the sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

As gelatin, besides general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japan Society of Science Photography (Bull. Soc. Sci. Pho.
t. Japan), No. 16, page 30 (1966), and an enzyme-treated gelatin may be used, or a hydrolyzate of gelatin may be used.

In the light-sensitive material of the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples thereof include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol-based compounds (dimethylol urea, etc.). Active halogen compounds (2,4-dichloro-6-hydroxy-1,3,5-
Triazine and its sodium salt, etc. and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ethane, bis (vinylsulfonylmethyl) ether or vinylsulfonyl groups as side chains Is preferred since a hydrophilic colloid such as gelatin can be rapidly cured to provide stable photographic characteristics. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3
-Pyridinio) methanesulfonate and the like, and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) also have a fast curing rate and are excellent.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, ie, indolenine A nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization. In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbenzene compounds substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde condensate (for example, U.S. Pat. No. 3,743,510) ), Cadmium salts,
An azaindene compound may be included. U.S. Patent No. 3,
615,613, 3,615,641, 3,617,295, 3,635,7
The combination described in No. 21 is particularly useful.

The silver halide photographic emulsion used in the present technology should contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the photosensitive material, or stabilizing the photographic performance. Can be. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; Azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes, pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonate, benzenesulfonate, benzenesulfonate and the like Can be added.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aids, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (for example, acceleration of development, high contrast, sensitization). May be.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye, or for the purpose of preventing irradiation or halation and other various purposes. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used.In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on a support. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of arrangement of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive layers, blue-sensitive layer, green-sensitive layer and red-sensitive layer or in order of blue-sensitive, red-sensitive and green-sensitive layers. Any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity, or may be composed of three layers to further improve the graininess. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer of fine silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity.

Generally, the cyan-sensitive coupler is contained in the red-sensitive emulsion layer, the magenta-forming coupler is contained in the green-sensitive emulsion layer, and the yellow-forming coupler is contained in the blue-sensitive emulsion layer. For example, a combination of infrared-sensitive layers may be used for pseudo color photographic quality or semiconductor laser exposure.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of a flexible support such as a plastic film, paper, cloth, etc., or a glass, pottery,
It is applied to a rigid support such as metal. Useful as flexible supports are cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
Examples thereof include a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate and polycarbonate, a baryta layer, and paper coated or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with a photographic emulsion layer or the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used. U.S. Pat.No. 2,681,294 as required,
Multiple layers may be simultaneously coated by the coating methods described in JP-A-2761791, JP-A-3526528 and JP-A-3508947.

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color paper, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure, No.17123 (1978
July, 1999) or by using a black color coupler described in U.S. Pat. No. 4,126,461 and British Patent No. 2,102,136 to obtain a black-and-white image such as for X-rays. The present invention can be applied to a photosensitive material. For plate making film such as lith film or scanner film, direct medical, indirect medical or industrial X-ray film, negative black and white film for photography, black and white photographic paper, COM or ordinary micro film, and printout type photosensitive material The present invention can also be applied.

Various exposure means can be used for the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps, and strobe or metal burning flash bulbs are common. It occurs in the wavelength range from ultraviolet to infrared,
Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources can also be used as recording light sources. Also, a micro-shutter array using a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or lanthanum-doped lead zirconate titanate (PLZT), etc. Exposure means combining a linear or planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also effective as the color developing agent, but p-
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β
-Methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These diamines are generally more stable in a salt than in a free state, and are preferably used.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a development inhibitor such as bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds or an antifoggant. It generally contains an agent and the like. If necessary, preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dyes Forming couplers, competing couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity enhancers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos Various chelating agents represented by carboxylic acids,
An antioxidant described in West German Patent Application (OLS) No. 2,622,950 may be added to the color developer.

In the development process of the reversal color photosensitive material, color development is usually performed after black-and-white development is performed. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or N
Known black-and-white developers such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. In order to further speed up the processing, a processing method of performing a bleach-fixing process after the bleaching process may be used. Examples of the bleaching agent include iron (III), cobalt (III), chromium (I
Compounds of polyvalent metals such as V) and copper (II), peracids, quinones, nitrones and the like are used. Typical bleaching agents include pheiliocyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid and the like. Aminopolycarboxylic acids or citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates; manganates; nitrosophenols and the like can be used. Of these, iron (III) ethylenediaminetetraacetate, iron (III) diethylenetriaminepentaacetate and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Further, the iron (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution or a single-bath bleach-fixing solution.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,
No. 988, JP-A-53-32736, JP-A-53-57831, JP-A-37418
No. 53-65732, No. 53-72623, No. 53-95630,
No. 53-95631, No. 53-104232, No. 53-124424, No. 5
Compounds having a mercapto group or a disulfide group described in 3-141623, 53-28426, Research Disclosure No. 17129 (July 1978);
Thiazolidine derivatives as described in JP 140129; JP-B-45-8506; JP-A-52-20832; JP-A-53-32735;
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodides described in JP-A-58-16235; Polyethylene oxides described in West German Patents 966,410 and 2,748,430; Polyamine compounds described in JP-A-83836; and JP-A-49-42434 and JP-A-49-59644.
And the compounds described in JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940 can also be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,290,812
And the compounds described in JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred.
These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

Examples of the fixing agent include thiosulfate, thiocyanate, thioether-based compound thioureas, and a large amount of iodide, and thiosulfate is generally used. As a preservative for the bleach-fixing solution or the fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

After the bleach-fixing process or the fixing process, a washing process and a stabilizing process are usually performed. In the washing step and the stabilization step, various known compounds may be added to prevent precipitation, conserve water, and the like. For example, to prevent precipitation
Hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid; fungicides and antibacterial agents for preventing the occurrence of various bacteria, algae and mold; magnesium salts and aluminum salts bismuth salts Metal salts represented by the formula (1), a surfactant for preventing drying load and unevenness, various hardeners, and the like can be added as necessary. Or West, Photographic Science and Engineering (LEWest, Pho
t. Sci. Eng.), Vol. 6, pages 344-359 (1965) and the like. In particular, the addition of a chelating agent or an anti-binder is effective.

In the water washing step, two or more tanks are generally countercurrently washed to save water. Furthermore, instead of the washing step, Japanese Patent Laid-Open No.
A multi-stage countercurrent stabilization step as described in -8543 may be performed. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (for example, pH 3 to 9) Aldehydes such as monocarboxylic acid, dicarboxylic acid, and polycarboxylic acid) and formalin. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzoisothiazolinone, irithiazolone, 4- Various additives such as thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, and hardeners may be used, and the same or different target compounds may be used. May be used in combination of two or more.

Also, ammonium chloride as a membrane pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

In the color light-sensitive material for photographing, the step (washing-stabilization) usually performed after fixing can be replaced with the above-mentioned stabilizing step and washing step (water saving processing). On this occasion,
When the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilizing treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, depending on the type of the photographic material and the processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Patent No. 3,342,59
No. 7, indoaniline-based compound, No. 3,342,599,
Research Disclosure Nos. 14850 and 15159, Schiff base compounds, the aldol compounds described in 13924, metal salt complexes described in U.S. Pat.No. 3,719,492,
Including the urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-56-16133, and JP-A-56-59232.
No. 56-67842, No. 56-83734, No. 56-83735,
56-83736, 56-89735, 56-81837, 56
-54430, 56-106241, 56-107236, 57-9
Examples of the precursors include various salt-type precursors described in Nos. 7531 and 57-83565.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547 and JP-A-57-21114.
No. 7, No. 58-50532, No. 58-50536, No. 58-50533,
Nos. 58-50534, 58-50535 and 58-115438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but higher temperatures can accelerate processing and reduce processing time, and conversely, lower temperatures can improve image quality and improve processing solution stability. it can. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

A heater, a temperature sensor, a liquid level sensor, a circulating pump, a filter, a floating pig, a squeegee, and the like may be provided in the various treatment baths as needed.

In the case of continuous processing, a certain finish can be obtained by using a replenisher of each processing liquid to prevent fluctuation of the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction and the like.

When the light-sensitive material of the present invention is a color paper, it can be subjected to a bleach-fixing process, if necessary, even if it is a color photographic material for photography.

(Examples) Next, the present invention will be described in more detail based on examples.

Example 1 (Preparation of silver halide emulsion) 32 g of lime-processed gelatin was added to 1000 ml of distilled water,
After dissolving in, 3.3 g of sodium chloride is added and the temperature is 52 ° C
Was raised. To this solution, 3.2 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. Subsequently, a liquid in which 32.0 g of silver nitrate was dissolved in 200 ml of distilled water and a liquid in which 11.0 g of sodium chloride was dissolved in 200 ml of distilled water were added and mixed over 14 minutes while maintaining the temperature at 52 ° C. Further, a solution prepared by dissolving 128.0 g of silver nitrate in 560 ml of distilled water and sodium chloride 4
4.0 g, 0.1 mg of potassium hexachloroiridate (IV)
Is dissolved in 560 ml of distilled water.
The mixture was added over a period of minutes. Keep at 52 ℃ for 15 minutes, then at 40 ℃
, And the mixture was desalted and washed with water. Further, lime-processed gelatin was added to obtain an emulsion (A). The resulting emulsion contained cubic silver chloride grains having an average grain size of 0.45 µ and a coefficient of variation in grain size distribution of 0.08.

In the emulsion (A), the aqueous sodium chloride solution added together with the aqueous silver nitrate solution was changed to a mixed solution of sodium chloride and potassium bromide (total molar number was the same, and the molar ratio was 98: 2). A silver chlorobromide emulsion (B) containing mol% of silver bromide was obtained. The addition time of the reaction solution was adjusted so that the average grain size of the silver halide grains contained in the emulsion was equal to that of the emulsion (A). The obtained particles were cubic and the coefficient of variation of the particle size was 0.08.

In the emulsion (A), an aqueous sodium chloride solution to be added together with the aqueous silver nitrate solution was changed to a mixed solution of sodium chloride and potassium bromide (total molar number was the same, and the molar ratio was 9: 1) to change the molar ratio to 10 mol. % Silver bromide emulsion (C). The addition time of the reaction solution was adjusted so that the average grain size of the silver halide grains contained in the emulsion was equal to that of the emulsion (A). The obtained particles were cubic and the coefficient of variation of the particle size was 0.09.

After adjusting the pH and pAg of the three types of emulsions thus obtained, triethylthiourea was added to each of them for optimal chemical sensitization to give (A-1), (B-1) and (C-1).
Emulsion was obtained.

Separately, a fine grain silver bromide emulsion having an average grain size of 0.05 μm (a-1 (containing 2.5 × 10 ⁻⁵ mol of potassium hexairidium (IV) hexachloride per mol of silver bromide)) was prepared.

An emulsion (a-1) was added in an amount equivalent to 2 mol% of silver halide to the emulsion (A), and then triethylthiourea was added to prepare an emulsion which was optimally chemically sensitized.
(A-2).

These four types of silver halide emulsions each contain the following compounds as stabilizers in an amount of 5.0 × 10 5 per mol of silver halide.
^-4 mol was added.

Stabilizer (I-1) The halogen composition and distribution of the obtained four types of silver halide emulsions were examined by X-ray diffraction.

As a result, emulsion (A-1) was 100% silver chloride, emulsion (B-1) was 98% silver chloride (2% silver bromide), and emulsion (C-1) was 90% silver chloride ( (10% silver bromide). In contrast, emulsion (A-2) had a main peak of 100% silver chloride and 70% of silver chloride (30% silver bromide).
%), And a broad sub-peak could be observed with a tail extending to around 60% of silver chloride (40% of silver bromide).

(Dispersion of Solid Fine Particles of Compound of the Present Invention) Crystals of the compound of the present invention having the following composition were kneaded, and pulverized by a sand mill into fine particles (having an average diameter of 0.15 μm or less). Furthermore, the sand used was dispersed in 25 ml of a 10% lime-processed gelatin aqueous solution containing 0.1 g of citric acid, and the sand was used for glass / glass.
It was removed using a filter. The compound of the present invention adsorbed on the sand on the glass filter with hot water is also washed away and reduced by 7%.
100 ml of an aqueous gelatin solution was obtained. This is used as a solid fine particle dispersion of the compound of the present invention.

Dispersion A Compound (I-1) of the present invention: 1.2 g (I-5): 1.2 g 5% aqueous solution of surfactant (Cpd-10): 5 ml Dispersion B Compound B of the present invention (I-4) ... 1.2 g 〃 (I-15) ... 1.2 g Surfactant (Cpd-10) 5% aqueous solution ... 5 ml Dispersion C Compound (I-1) of the present invention ... 1.2 g Surfactant (Cpd-11) 5 % Aqueous solution… 5 ml (preparation of color light-sensitive material) Next, an emulsified dispersion such as a coupler was prepared, combined with each silver halide emulsion, and coated on a paper support laminated on both sides with polyethylene. A multi-layer color light-sensitive material having the above constitution was prepared.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ; ml / m ² for the solvent). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The polyethylene in the emulsion layer contains a white pigment (TiO ₂ ) and a bluish dye (ultra blue)] First layer (anti-halation layer) Gelatin 0.80 Dye (solid fine particle dispersion) (Table 1) Second Layer (yellow color-forming layer) Silver halide emulsion (Table 1) 0.30 Spectral sensitizing dye (Table 1) Yellow coupler (Y-1) 0.82 Color image stabilizer (Cpd-7) 0.09 Solvent (Solv6) 0.28 Gelatin 1.75 Third layer (color mixture preventing layer) Gelatin 1.25 Filter dye (Dye-4) 0.01 Color mixture inhibitor (Cpd-4) 0.11 Solvent (Solv2) 0.24 (Solv5) 0.26 Fourth layer (magenta coloring layer) Silver halide emulsion (No. Table 1) 0.12 Spectral sensitizing dye (Table 1) Supersensitizer (Table 1) Magenta coupler (M-1) 0.13 Magenta coupler (M-2) 0.09 Color image stabilizer (Cpd-1) 0.15 (Table 1) Cpd-8) 0.02 (Cpd-9) 0.03 Solvent (Solv1) 0 .34 (Solv2) 0.17 Gelatin 1.25 Fifth layer (ultraviolet absorbing layer) Gelatin 1.58 Filter dye (Dye-5) 0.05 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv3) 0.26 Six layers (cyan coloring layer) Silver halide emulsion (Table 1) 0.23 Spectral sensitizing dye (Table 1) Supersensitizer (Table 1) Cyan coupler (C-1) 0.32 Color image stabilizer (Cpd) -5) 0.17 (Cpd-6) 0.04 (Cpd-7) 0.40 Solvent (Solv4) 0.15 Gelatin 1.34 7th layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-4) 0.02 Solvent (Solv3) 0.09 Eighth layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 As a gelatin hardener for each layer, 1-oxy-3,5-
14.0 mg of dichloro-s-triazine sodium salt was used per 1 g of gelatin.

3.5 × 10 ^-5 mol was added per 1 mol of silver halide. And Cpd-12 were used in combination of 2.6 × 10 ⁻³ mol / Ag.

1.7 × 10 ^-5 mol and Cpd-12 per mol of silver halide
Was used in combination with 2.6 × 10 ^-3 mol / Ag and 1 × 10 ^-3 mol / Ag of Cpd-13.

The above samples were given laser exposure. For samples using Dye-1, Dye-2, and Dye-3 as sensitizing dyes, the laser exposure apparatus shown as exposure apparatus-1 was used.

 The exposure apparatus used in the embodiment is shown below.

(Exposure device-1) Semiconductor laser AlGaInP (oscillation wavelength,
Semiconductor laser GaAlAs (oscillation wavelength, about 750n)
m), GaAlAs (oscillation wavelength, about 830 nm) was used. The laser beam was rotated by a rotating polyhedron to assemble an apparatus capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to the scanning direction. For the exposure amount, the exposure time of the semiconductor laser was electrically controlled. (The exposure apparatus used in the present invention is described in detail in the specification of Japanese Patent Application No. 63-226552 filed by the present applicant.) Using the above-described exposure apparatus-1, a light beam wavelength of about 670 nm and a wavelength of about 750 are used.
Exposure was performed by adjusting the output with a semiconductor laser beam of about 830 nm and a laser beam of about 830 nm so that the line width of each was about 50 μm. The image was developed through the following processing steps.

On the other hand, a chart for CTF measurement was brought into close contact with each sample, and exposed for resolution measurement. The illumination used was a bandpass filter IF-8 manufactured by Nippon Vacuum Optical Co., Ltd. as a xenon light source.
After passing through filters having the maximum transmission wavelengths of the molds of 670 nm, 750 nm and 830 nm, the light amount was adjusted using an ND filter. The exposure time was about 10 ^-4 seconds. The image was developed through the following processing steps. The obtained yellow, magenta and cyan color images were measured using a micro reflection densitometer at 5 μm × 40.
The concentration was measured with a 0 μm aperture to obtain a CTF curve.

Table 2 shows the sharpness of the edge of the line drawing obtained by the exposure with the semiconductor laser beam and the value of the number of lines / mm at a CTF value of 0.5.

The processing steps used and the composition of each processing solution are shown below. Processing temperature Time Color development 35 ° C 45 seconds Bleaching and fixing 30-35 ° C 45 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Drying 70-80 ° C for 60 seconds (Rinse → Three tank countercurrent method.) The composition of each processing solution is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylphosphonic acid 1.5 g Triethylenediamine (1,4 diazabicyclo [2,2,2] octane) 5.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N-diethylhydroxylamine 4.2 g Optical brightener (UVITEX CK Ciba-Geigy) 2.0 g water In addition 1000 ml pH (25 ℃) 10.10 Bleaching fixer Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 18g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 3g Ammonium bromide 40g Glacial acetic acid 8g Add water 1000ml pH (25 ℃) 5.5 Rinse solution Ion exchange water (Calcium and magnesium are 3ppm or less each) According to the present invention, resolving power and sharpness of an edge can be remarkably improved. In particular, Sample-4 and Sample 6 show excellent edge breakage over yellow, magenta, and cyan images. In Sample-6, the second layer (cyan color development) had a slightly lower sensation, but particularly, the saturation of yellow, magenta, and cyan images was high (good color separation), and an excellent image was obtained.

In addition, none of the samples of the present invention had any color contamination due to the residual color due to the compound of the present invention, and whiteness equivalent to that of sample 1 of the comparative example was obtained.

Example 2 50 g of gelatin was dissolved in water, 30 ml of a 4% by weight aqueous solution of sodium dodecylbenzenesulfonate was used as a surfactant, and 1% of 1-hydroxy-3,5-dichlorotriazine sodium salt was used as a hardener. 45% aqueous solution
Further, the following solid fine particle dispersion of the compound of the present invention was added. That is, the crystals of the compound of the present invention were kneaded and pulverized by a sand mill into fine particles (having an average diameter of 0.15 μm or less). The dispersion was dispersed in 25 ml of a 10% lime-treated gelatin aqueous solution containing 0.1 g of citric acid, and the sand used was removed using a glass filter. The compound adsorbed on the sand on the glass filter was also washed off with hot water to obtain 100 ml of a 7% gelatin aqueous solution.

Dispersion A Compound (I-7) of the present invention: 0.9 g Surfactant (Cpd-10 of Example 1) 5% aqueous solution: 5 ml Dispersion B Compound of the present invention (I-15): 0.9 g Surface activity 5% aqueous solution of the agent (Cpd-10 of Example 1) 5 ml On the other hand, for comparison, a solution of the following dye a was added to the above I-8, I-8
The same amount as -15 was added to adjust the total amount to 1. This gelatin-containing aqueous solution was applied onto a polyethylene-coated paper support so that the dry film thickness was 4 μm. On the other hand, a silver chloroiodobromide (bromine content: 30 mol%, modal content: 0.1 mol%, average silver halide diameter: 0.30 micron) emulsion chemically sensitized with gold and sulfur compounds was added to 1 kg of the emulsion as follows.
Example 1 was added with 50 ml of a 0.05% by weight methanol solution of -7.
30 ml of a 1.0% by weight methanol solution of Cpd-12 in Example 1
20 ml of a 0.5% by weight solution of Cpd-13 and 40 ml of a 0.6% by weight solution of the following Cpd-14 were added, and 30 ml of a 4.0% by weight aqueous solution of sodium dodecylbenzenesulfonate was added thereto, and 1-hydroxy-3,5-dichlorotriazine sodium salt was added. 35 ml of a 1.0% by weight aqueous solution was added and stirred, and the mixture was applied on the gelatin-coated surface of the support. Further, an aqueous solution containing gelatin and sodium dodecylbenzenesulfonate was applied thereon as a protective layer.

Each of the films thus prepared is exposed with a (A) light emitting diode having a wavelength of 760 nm and (B) a semiconductor laser having a wavelength of 783 nm, and is subjected to an automatic developing machine FG-800RA (manufactured by Fuji Photo Film Co., Ltd.) using a developer LD-835 manufactured by Fuji Photo Film. The treatment was performed at 38 ° C for 20 seconds.

Evaluation of image quality is 1 (many fringes and very poor image quality)
To 5 (no fringe, sharp image). The evaluation of the residual color was performed on a scale from 1 (very much residual color) to 5 (no residual color). In the case of evaluation of fringe and residual color, visual evaluation can be performed with higher sensitivity than measurement with an instrument, and visual evaluation is also performed when an actual photosensitive material is used.

 The results are shown in Table 3.

Comparative dye a is the following dye described in British Patent No. 434,875.

When the dispersion of the present invention is used as apparent from Table 3, good image quality and an image with little residual color can be obtained.

Example 3 After a corona discharge treatment on a paper support laminated on both sides with polyethylene, paper support samples A, B and C were obtained using a gelatin subbing layer or the following dispersion of the compound of the present invention.

(Dispersion method of compound of the present invention) Crystals of the compound of the present invention shown below were kneaded, and finely divided by a sand mill. Further, the dispersion was dispersed in 25 ml of a 10% lime-treated gelatin aqueous solution containing 0.5 g of citric acid, and the sand used was removed using a glass filter. Compound I-12 of the present invention: 0.8 g The attached compound was removed, and 100 ml of a 7% gelatin solution was added. (The average particle size of the fine particles was 0.15 μm.) Paper support A Undercoat layer Gelatin: 0.8 g / m ² Paper support B: Anti-halation layer Gelatin: 0.6 g / m ² Dye (1) 25 mg / m ² Compound of the present invention I-12: 40 mg / m ² Paper support C Anti-halation layer Gelatin: 0.6 g / m ² Dye (1): 40 mg / m ² Compound I of the present invention -12... Multilayer color photographic paper samples 4-1 to 4-4 having the following layer constitution were obtained on paper support samples A, B and C at 65 mg / m ² .

 The coating solution was prepared as follows.

Preparation method of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate in 4.4 g and (Cpd-7) 1.8 g
Then, 4.1 g of each of the solvents (Solv-3) and (Solv-6) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (80.0 mol%, cubic, having an average grain size of 0.85 μ, variation coefficient of 0.08,
Mol%, cube, average particle size 0.62μ, coefficient of variation 0.07
Blue sensitizing dye shown below per 1 mol of silver to sulfur sensitized mixture of
One with 5.0 × 10 ^-4 mol added was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-
s-Triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

Blue-sensitive emulsion layer (5.0 × 10 ^-4 mol per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) Red-sensitive emulsion layer (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer at 2.6 × 10 ⁻³ mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer per mole of silver halide.
4.0 × 10 ^-6 mol, 3.0 × 10 ^-5 mol, 1.0 × 10 ^-5 mol, and 2-methyl-5-t-octylhydroquinone in an amount of 8 × 10 ^-3 mol and 2 × 10 ^-3 mol per mol of silver halide, respectively. ^-2 ,
2 × 10 ^{-2 was} added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 ×
10 ^-2 mol was added.

To one of the paper support samples A, the following comparative dye was added to the undercoat layer.

and (Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support A-4, Samples A, B and C in which an undercoat layer and an anti-halation layer were provided on a polyethylene-laminated paper [polyethylene on the first layer side containing a white pigment (TiO ₂ ) and a bluish dye (ultra blue)]
Seed First layer (blue-sensitive layer) Silver chlorobromide emulsion (AgBr: 80 mol%) 0.26 Gelatin 1.83 Yellow coupler (ExY) 0.83 Color image stabilizer (Cpd-1) 0.19 0.1 (Cpd-7) 0.08 Solvent (Solv-3) 0.18〃 (Solv-6) 0.18 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-6) 0.08 Solvent (Solv-1) 0.16〃 (Solv-4) 0.08 Third layer ( Green sensitive layer) Silver chlorobromide emulsion (AgBr 90 mol%, cube, average grain size)
0.47μ, coefficient of variation 0.12 and AgBr90 mol%, cubic, average particle size 0.36μ, coefficient of variation 0.09:
0.16 Gelatin 1.79 Magenta coupler (ExM) 0.32 Color image stabilizer (Cpd-3) 0.20〃 (Cpd-8) 0.03〃 (Cpd-4) 0.01〃 (Cpd-9) 0.04 Solvent (Solv-2) 0.65 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red sensitive layer) ) Salt collection silver (AgBr 70 mol%, cube, average particle size 0.49
μ, variation coefficient 0.08 and AgBr 70 mol%, cubic, average particle size 0.34μ, variation coefficient 0.10 are mixed in a ratio of 1: 2 (Ag molar ratio) 0.23 gelatin 1.34 cyan coupler (ExC) 0.30 color Image stabilizer (Cpd-6) 0.17 〃 (Cpd-7) 0.40 Solvent (Solv-6) 0.20 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic of polyvinyl alcohol 0.17 Modified copolymer (17% modification degree) Liquid paraffin 0.03 (Cpd-1) color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing inhibitor (Cpd-6) color image stabilizer (Cpd-7) Color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Color image stabilizer (UV-1) UV absorber (Solv-1) Solvent (Solv-2) Solvent (Solv-3) Solvent (Solv-4) Solvent (Solv-5) Solvent (Solv-6) Solvent (ExY) Yellow coupler (ExM) Magenta coupler (ExC) Cyan coupler For the obtained samples 4-1 to 4-4, a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, color temperature of light source 3,2)
00 ° K) to give sensitometric step exposures through the blue, green and red filters. On the other hand, exposure for measuring the resolution (CTF) was performed, and then the following development processing was performed. The concentration of the obtained sample was measured, and the results shown in Table 5 were obtained.

(Processing process) Processing process temperature Time Color development 37 ° C 3 minutes 30 seconds Bleaching and fixing 33 ° C 1 minute 30 seconds Rinse 24-34 ° C 3 minutes Dry 70-80 ° C 1 minute (Processing solution) Color developing solution Water 800 ml diethylenetriaminepentaacetic acid 1.0 g nitrilotriacetic acid 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid (60% solution) 1.0 ml benzyl alcohol 15 ml diethylene glycol 10 ml sodium sulfite 2.0 g potassium bromide 1.0 g potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5 g hydroxylamine sulfate 3.0 g Optical brightener (WHITEX4, manufactured by Sumitomo Chemical) 1.0 g 1000 ml pH (25 ℃) 10.25 bleach-fixing solution water 400ml ammonium thiosulfate (700 g /) 150 ml sodium sulfite 18g ethylenediaminetetraacetic acid iron (III) ammonium 55g disodium ethylenediaminetetraacetate isocyanatomethyl Um 5g water 1000ml pH (25 ℃) was added 6.70 as washing water below, the ion-exchange-treated water tap water and deionized by ion exchange fat, calcium, magnesium and 3ppm or less, further dichloride It was used after adding 20 ppm of sodium isocyanurate. The pH of this water was 6.6.

When the compound according to the present invention is used in the anti-halation layer, the sensitivity is relatively small and the residual color is insignificant. By using such an amount, the resolving power can be remarkably improved.

Rapid developable color photographic paper obtained by using support samples B and C and providing a high-temperature silver emulsion layer thereon (EP 273429).
No. 273430 and Japanese Patent Application No. 63-7861) having the multilayer structure) can obtain similar results.

Example 4 The blue-sensitive emulsion used in Example 3 was replaced with a silver chlorobromide emulsion having a silver bromide content of 0.6 mol% (cubic, average grain size 0.8 μm, variation coefficient 0.08), and a green-sensitive emulsion was replaced with a silver bromide content. 1.2 mol% silver chlorobromide emulsion (cubic, average grain size 0.42μ coefficient of variation
0.07), a red-sensitive emulsion layer was added to a silver chlorobromide emulsion with a silver bromide content of 1.5 mol% (cube, average grain size 0.45μ variation coefficient)
0.07), and samples 5-1 to 5-4 corresponding to samples 4-1 to 4-4 were prepared in the same manner as in Example 3.

Each of the blue-sensitive, green-sensitive, and red-sensitive emulsions contains the following spectral sensitizing dye and Cpd-10, and silver bromide exists as a localized phase in a part of grains.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (4.0 × 10 ^-4 mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) Red-sensitive emulsion layer (0.9 × 10 ^-4 mol per mol of silver halide) (Each emulsion was added in an amount of 5 × 10 ⁻⁴ mol per mol of silver halide.) Using the obtained photographic materials, the same test as in Example 3 was carried out by the following processing solutions and processing steps. Sample 5-4 was higher in sensitivity than the sample 5-2 in the red-sensitive layer and the green-sensitive layer. In addition, Dmin of each of Samples 5-3 and 5-4 was as low as that of Sample 5-2, and the resolving power was higher than that of the other samples as follows.

Process temperature Time Color development 35 ° C. 45 seconds blix 30 to 36 ° C. 45 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 30 seconds Drying 70 85 ° C for 60 seconds (4 tank countercurrent system to stable). The composition of each processing solution is as follows.

Color developer Water 800 ml Ethylenediaminetetraacetic acid 2.0 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N-diethylhydroxylamine 4.2g 5,6-dihydroxybenzene-1,2,4-trisulfonic acid 0.3g Optical brightener (4,4'-diaminostilbene) 2.0g Add water 1000ml pH 10.10 Bleaching fixer Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 18g Iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 3g Glacial acetic acid 8g Add water 1000ml pH 5.5 Stabilizer Formalin (37%) 0.1 g Formalin-sulfuric acid adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazo Down-3-on 0.01 g by addition of copper sulfate 0.005g water 1000 ml pH 4.0 Example 5 subbing subjected to cellulose triacetate film support, a multi-layer color light-sensitive material consisting of layers of the following compositions A sample 601 was manufactured.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer. In the chemical structural formulas, those in the form of a salt conformed to the notation of Chemical Abstract.

First layer (anti-halation layer) Black colloidal silver 0.15 gelatin 1.9 UV-1 (ultraviolet absorber) 0.03 UV-2 (ultraviolet absorber) 0.06 UV-3 (ultraviolet absorber) 0.07 Solv-2 ( Solvent) ... 0.08 ExF-1 (cyan dye) ... 0.01 ExF-2 (cyan dye) ... 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) AgI 4 mol% Uniform Sphere equivalent diameter 0.4μ sphere equivalent diameter variation 37 %, Tabular grain diameter / thickness ratio 3.0 coated silver amount ... 0.4 gelatin ... 0.8 EXS-1 (sensitizing dye) ... 4.0 x ^10-4 EXS-2 (sensitizing dye) ... 0.1 x ^10-4 EXS-5 ( Sensitizing dye) ... 6.5 x ^10-4 EXS-7 (sensitizing dye) ... 6.5 x ^10-4 EXC-1 (cyan coupler) ... 0.17 EXC-2 (cyan coupler) ... 0.05 EXC-3 (magenta colored cyan coupler) 0.09 Third layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 2: 1, internal high AgI sphere equivalent diameter 0.65μ, change in sphere equivalent diameter) Coefficient 25%, tabular grain, diameter / thickness ratio 2.0) coating silver amount ... 0.55 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, sphere-corresponding diameter 0.
4μ, Coefficient of variation of sphere equivalent diameter 37%, spherical particles, diameter / thickness ratio 3.0) Coating silver amount: 0.1 Gelatin: 1.0 EXS-1 (sensitizing dye) ... 5.0 × 10 ^-4 EXS-2 (sensitizing dye) … 0.2 × 10 ^-4 EXS-5 (sensitizing dye)… 8.2 × 10 ^-4 EXS-7 (sensitizing dye)… 8.2 × 10 ^-4 ExC-1 (cyan coupler)… 0.31 ExC-2 (cyan coupler) ... 0.01 ExC-3 (magenta colored cyan coupler) ... 0.09 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with core shell ratio 2: 1, equivalent sphere diameter 0.7) μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio 2.5) Silver coating amount: 0.9 Gelatin: 0.8 EXS-1 (sensitizing dye) 6.4 × 10 ^-4 EXS-2 (sensitizing dye) ) 0.9 x ^10-4 EXS-5 (sensitizing dye) 10.4 x ^10-4 EXS-7 (sensitizing dye) 10.4 x ^10-4 ExC-1 (cyan coupler) 0.07 ExC-4 (cyan coupler) )… 0.08 Solv-1 (solvent)… 0.07 Solv 2 (solvent) ... 0.07 Solv-3 (〃) ... 0.02 CPD (antifoggant) ... 4.6 × 10 ^-4 fifth layer (intermediate layer) Gelatin ... 0.6 UV-4 (ultraviolet absorber) ... 0.03 UV-5 (Ultraviolet absorber) 0.04 Cpd-1 (color mixture inhibitor) 0.1 Polyethyl acrylate latex 0.08 Solv-1 (solvent) 6th layer (low sensitivity green-sensitive emulsion layer) 4 mol% of silver iodobromide AgI Uniform type. Sphere equivalent diameter 0.4μ, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 37%, plate-like particles, diameter / thickness ratio 2.0 Coating silver amount 0.18 Gelatin 0.4 ExS-3 (sensitizing dye) 2 × 10 ^-4 ExS-4 (sensitizing dye) ... 7 x 10 ^-4 ExS-5 (sensitizing dye) ... 1 x 10 ^-4 ExM-5 (magenta coupler) ... 0.11 ExM-7 (yellow colored magenta coupler) ... 0.03 ExY-8 (DIR coupler) 0.01 Solv-1 (solvent) 0.09 Solv-4 (solvent) 0.01 Seventh layer (intermediate-speed green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1) 1: 1 surface height AgI type, sphere equivalent type, sphere equivalent diameter 0.5μ, coefficient of variation of sphere equivalent diameter 20%, plate-shaped particles, diameter / thickness ratio 4.0 coated silver amount 0.27 gelatin… 0.6 ExS-3 (sensitized Dye) 2 × 10 ^-4 ExS-4 (sensitizing dye) 7 × 10 ^-4 ExS-5 (sensitizing dye) 1 × 10 ^-4 ExM-5 (magenta coupler) 0.17 ExM-7 (yellow) Colored magenta coupler 0.04 ExY-8 (DIR coupler) 0.02 Solv-1 (solvent) 0.14 Solv-4 (solvent) 0.02 Eighth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 8.7 mol%, Multilayer structure particles having a silver content ratio of 3: 4: 2, 24 mol from the inside of the AgI content, 0 mol%, 3 mol%, equivalent spherical diameter 0.7 μ, coefficient of variation of equivalent spherical diameter 25%, plate-like particles, diameter / Thickness ratio 1.6) Coating amount of silver: 0.7 Gelatin: 0.8 ExS-4 (sensitizing dye): 5.2 × 10 ^-4 ExS-5 (sensitizing dye): 1 × 10 ^-4 ExS-8 (sensitizing dye): 0.3 × 10 ^-4 ExM-5 (magenta coupler) ... 0.1 ExM-6 (yellow colored magenta coupler) ... 0.03 ExY-8 (DIR coupler) ... 0.02 ExC-1 (cyan coupler) ... 0.02 ExC-4 (cyan coupler) ... 0.01 Solv-1 (solvent) ... 0.25 Solv-2 (solvent) ... 0.06 Solv-4 (solvent) ... 0.01 Cpd-7 (antifoggant) ... 1 x 10 ^-4 9th layer (intermediate layer) Gelatin ... 0.3 Cpd -1 (Anti-color mixing agent) 0.04 Polyethyl acrylate latex 0.12 Solv-1 (solvent) 0.02 10th layer (donor layer having a multilayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 2) 1: 1 internal high AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grain, diameter / thickness ratio 2.0) Silver coating amount: 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform) Coefficient of variation of mold sphere equivalent diameter 37%, plate-like particles, diameter / thickness ratio 3.0) coated silver amount ... 0.19 gelatin ... 1.0 ExS-3 (sensitizing dye) ... 6 x 10 ^-4 ExM-10 (DIR coupler) 0.19 Solv-1 (solvent) ... 0.20 Solv-3 ... 0.05 Layer 11 (yellow filter layer) Yellow colloidal silver ... 0.06 Gelatin ... 0.8 Cpd-2 (yellow dye) ... 0.13 Solv-1 (solvent) ... 0.13 Cpd-1 ( 0.07 Cpd-6 (antifoggant) 0.002 H-1 (hardener) 0.13 12th layer (low-sensitivity blue-sensitive emulsion layer) iodobromide Silver emulsion (AgI 4.5 mol%, uniform AgI type, equivalent sphere diameter)
0.7μ, sphere equivalent diameter variation coefficient 15%, plate-like grains, diameter / thickness ratio 7.0) Silver coating amount: 0.5 silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere equivalent diameter 3.
0 μ, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter / thickness ratio 7.0) Coating silver amount: 0.25 Gelatin: 1.8 ExS-6 (sensitizing dye): 9 × 10 ^-4 ExC-1 (cyan coupler) ... 0.06 ExC-4 (cyan coupler) ... 0.03 ExY-9 (DIR coupler) ... 0.14 ExY-11 (yellow coupler) ... 0.89 Solv-1 (solvent) ... 0.42 Layer 13 (intermediate layer) Gelatin ... 0.7 ExY-12 (DIR coupler) 0.20 Solv-1 (solvent) 0.34 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter)
1.0μ, coefficient of variation of sphere equivalent diameter 25%, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Coating amount of silver: 0.5 Gelatin: 0.5 ExS-6 (sensitizing dye): 1 × 10 ^-4 ExY-9 (DIR coupler): 0.01 ExY-11 (yellow coupler): 0.20 ExC-1 ( Cyan coupler) 0.02 Solv-1 (solvent) 0.10 15th layer (first protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07μ) Silver coating amount 0.12 Gelatin 0.9 UV-4 (ultraviolet absorber) 0.11 UV-5 (ultraviolet absorber) 0.16 Solv-5 (solvent) ... 0.02 H-1 (hardener) 0.13 Cpd-5 (scavenger) 0.10 polyethyl Acrylate latex ... 0.09 16th layer (2nd protective layer) Fine grain silver bromide emulsion (2 mol% AgI, uniform AgI type, equivalent sphere diameter 0.07μ) Coating amount of silver ... 0.36 Gelatin ... 0.55 Polymethyl methacrylate particle diameter 1.5μ ... 0.2 H-1 (hardener) ... 0.17 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3.
(0.07 g / m ² ) Surfactant Cpd-4 (0.03 g / m ² ) was added as a coating aid.

x: y = 70: 30 (wt%) x: y: z = 50: 25: 25 molecular weight about 20,000 Cpd-10 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK (Preparation of Sample 602) Instead of the black colloidal silver of the first layer of Sample 601, the compound I-4 of the present invention (0.2 g / m ² ). A dispersion of the compound I-4 of the present invention was prepared by the following method.

3 ml of 5% aqueous sodium p-octylphenoxyethoxyethoxyethanesulfonate in water (21.7 ml) and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxy poly (degree of polymerization 10) oxyethylene ether was placed in a 700 ml pot mill,
1.00 g of the compound I-4 of the present invention and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed in a vibration ball mill for 2 hours. The vibration ball mill used was a BO type manufactured by Chuo Kakoki.

The contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and filtered to obtain a gelatin dispersion of the compound I-4 of the present invention.

(Preparation of Sample 603) A sample 602 was prepared in the same manner as the sample 602 except that the compound I-6 of the present invention was used instead of the compound I-4 of the present invention.

(Preparation of Sample 604) In Sample 602, Compound I-6 of the present invention (0.1 g / m ² ) was used instead of Compound I-4 of the present invention. (0.1 g / m ² ) was prepared in the same manner as in Sample 602 except that (0.1 g / m ² ) was simultaneously used.

(Preparation of sample 605) In sample 602, the following comparative compound 6-1 (compound described in JP-A-52-92716) (0.2 g / m ² ) was used in place of compound I-4 of the present invention. A sample was prepared in the same manner as in Sample 602 except for the above.

After exposing the samples 601 to 605 obtained as described above, they were processed by the methods shown in Table 7.

Next, the composition of the treatment liquid will be described.

Color developing solution (unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl- N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water, 1.0 L pH 10.05 Bleaching solution (unit: g) Ferric ethylenediaminetetraacetate Ammonium dihydrate 120.0 Sodium ethylenediaminetetrahydrate Salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0 ml Add water 1.0 L pH 6.3 Bleaching / fixing solution (unit: g) Ferric ethylenediaminetetraacetate ammonium dihydrate 50.0 Sodium ethylenediaminetetraacetate 5.0 Sodium sulfite 12.0 Aqueous ammonium thiosulfate (700 g /) 240.0ml Ammonia water (27%) 6.0ml Add water 1.0L pH 7.2 Rinse solution Tap water is exchanged with H type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH type anion exchange. Water is passed through a mixed-bed column filled with resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3 mg / L or less, followed by sodium diisocyanurate 20 mg / sodium sulfate 0.15 g / Was added. The pH of this solution is in the range 6.5-7.5.

Stabilizing solution (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Water was added to obtain 1.0 L pH 5.0-8.0. The sample was subjected to sensitometry and the results shown in Table 8 were obtained.

By using the fine particle solid dispersion of the compound of the present invention in the anti-halation layer, it is possible to obtain a color photographic light-sensitive material having no decrease in sensitivity, fogging, residual color of processing and a small amount of residual silver.

Example 6 In the preparation of Sample 601 in Example 5, the following compound I- of the present invention was used in place of the black colloidal silver in the first layer.
Replaced with 51 fine particle dispersions (coating amount: 0.2 g / m ² )
611 was created. The fine particle dispersion of the compound I-51 was prepared in the same manner as in the preparation of the fine particle dispersion of the compound I-4 described in Example 5, except that the compound I-4 was replaced with the compound I-51. Further, samples 612 to 612 were prepared in the same manner except that compound I-51 was replaced with the following compounds I-52, I-53, I-54 and I-55 of the present invention, and compounds A, B and C for comparison. Created 618.

(Compound 10 described in the upper column on page 6 of JP-A-63-316853) (Sample No. 10 on page 5 of JP-B-58-35544) (Sample No. 11 on page 5 of JP-B-58-35544) After exposing the sample 601 of Example 5 and the samples 611 to 619 obtained as described above, the method described in Example 5 was followed. Treated similarly.

Sensitometry was performed on the obtained treatment in the same manner as in Example 5, and the results shown in Table 9 below were obtained.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-316853 (JP, A) JP-A-55-155350 (JP, A) JP-A-56-12639 (JP, A) JP-A 63-16839 301888 (JP, A) JP-B-58-35544 (JP, B2) US Patent 4,092,168 (US, A) US Patent 4,102,688 (US, A)

Claims (2)

(57) [Claims] 1. A silver halide photographic material having a silver halide photographic emulsion layer and another hydrophilic colloid layer on a support, wherein the silver halide emulsion layer or the other hydrophilic colloid layer has the following general formula: A silver halide photographic light-sensitive material comprising a solid fine particle dispersion of the compound represented by the formula (I). General formula (I) Wherein R ₁ is p-carboxyphenyl, m-carboxyphenyl, o-carboxyphenyl, 3,5-dicarboxyphenyl, 2,4-dicarboxyphenyl, 2,5-dicarboxyphenyl Enyl, p-carboxybenzyl, m-carboxybenzyl, o-carboxybenzyl, a group selected from the group consisting of p-carboxyphenethyl and 2,4-dicarboxybenzyl, wherein R ₂ is a hydrogen atom, an alkyl group, an aryl group Represents a heterocyclic group, COR ₄ or SO ₂ R ₄ ;
₃ is a hydrogen atom, a cyano group, a hydroxyl group, a carboxylic acid group, an alkyl group, an aryl group, COOR ₄ , OR ₄ , NR ₅ R ₆ , CONR ₅ R ₆ , NR
₅ COR ₄ , NR ₅ SO ₂ R ₄ or NR ₅ CONR ₅ R ₆ (where R ₄ represents an alkyl group or an aryl group, and R ₅ and R ₆ represent a hydrogen atom, an alkyl group or an aryl group.) , L ₁ , L ₂ ,
L ₃ represents a methine group, and n represents 1 or 2. ] 2. The compound represented by the general formula (I) has a pH of 6
The silver halide photographic material according to claim 1, wherein the material is substantially water-insoluble below and water-soluble at a pH of 8 or more.